Polyfluoroalkylated alkenes and silicon compounds prepared therefrom

ABSTRACT

Novel polyfluoroalkylated alkenes compounds prepared therefrom are described.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage filing under 35 U.S.C. 371 ofPCT/US2015/044572, filed Aug. 11, 2015, which claims the benefit of U.S.Application No. 62/042,482, filed Aug. 27, 2014, the disclosure of whichis incorporated by reference in its/their entirety herein.

FIELD

This invention relates to methods of treating substrates (especiallysubstrates having a hard surface such as, for example, ceramics orglass) to impart water, oil, stain, and/or dirt repellency to a surfacethereof, and, in other aspects, this invention relates to compositionsfor use in the methods and to substrates treated thereby.

BACKGROUND

Various fluorochemical compositions have been used as coatingcompositions for application to substrates (for example, hard surfacesubstrates and fibrous substrates) to impart low surface energycharacteristics such as oil and/or water repellency (oleophobicityand/or hydrophobicity). When used in coatings or films, however, manyfluorochemical materials have tended to diffuse to the surface of thecoating or film and to become depleted over time (for example, due torepeated cleanings of the surface). This has led to the use offluorochemical derivatives having reactive or functional groups (forexample, perfluoropolyether thiols, silanes, phosphates, and acrylates)to enable covalent attachment to the coatings, films, or substratesurfaces.

Silane and silicone compounds having one or more fluorochemical groupshave been used (alone and in combination with other materials) toprepare surface treatment compositions for substrates such as glass andceramics. Such silane compounds have typically included one or morehydrolyzable groups and at least one polyfluorinated alkyl or polyethergroup.

Numerous fluorochemical surface treatments have been developed and havevaried in their ease of applicability to substrates (for example, due todifferences in viscosity and/or in solvent solubilities, some treatmentseven requiring expensive vapor deposition or multiple applicationsteps), in their requisite curing conditions (for example, somerequiring relatively high curing temperatures for relatively longperiods of time), in their repellency levels, in their ease of cleaning,in their degrees of optical clarity, and/or in their durability (forexample, in their chemical resistance, abrasion resistance, and/orsolvent resistance). Many have also been at least somewhatsubstrate-specific, requiring production of multiple compositions toensure adhesion to different substrates.

SUMMARY

There exists an ongoing need for surface treatment processes (andfluorochemical compositions for use therein) that can meet theperformance requirements of a variety of different surface treatmentapplications. Such processes will preferably be simple, cost-effective,compatible with existing manufacturing methods, and/or capable ofimparting repellency to a variety of different substrates.

Briefly, in one aspect, this invention provides a novel polyfluoroalkylalkenes and, derived therefrom, novel fluoroalkylsilicon compounds,including fluoroalkylsilicones and fluoroalkylsilanes. In another aspectthis disclosure provides a coating composition comprising thefluoroalkylsilicone compounds with high water repellency, as measure bythe receding water contact angle. In another aspect this disclosureprovides a process for making the fluoroalkylsilicone compounds. Inanother aspect, this disclosure provide a surface treatment processwhich comprises (a) providing at least one substrate having at least onemajor surface; coating the surface with the coating composition, andcuring the coating. In another aspect this disclosure provides thecoated articles which have high water contact angles, especiallyreceding water repellency.

The present disclosure provides novel fluoroalkyl silicon compounds thatcan be used as release materials or can also be blended with one or moreadditional low surface energy materials (e.g., fluoropolymers,polyacrylates with pendent R_(f) group, lower cost fluoroalkyl siliconesand non-fluorinated silicones) while maintaining the desired low releasecharacteristics of the instant fluorosilicone material. In addition, insome embodiments, high blend ratios of low surface energy materials maybe used without detrimentally affecting the re-adhesion force of theadhesive after removal of the blended release materials comprising thepresent fluoroalkyl silicon compounds.

DETAILED DESCRIPTION

In a first embodiment, the present disclosure provides novelpolyfluoroalkyl alkenes of the formula:[R_(f)—O—CHFCF₂—O]_(x)—R*—CH═CH₂,  IwhereinR_(f) is a perfluoroalkyl group, optionally substituted by one or morein-chain —O—, or —NR_(f) ¹-heteroatoms, where R_(f) ¹ is aperfluoroalkyl;subscript x is at least two; andR* is (hetero)hydrocarbyl group of valence x+1, and is preferablyselected from C2-C10 alkylene.

The R_(f) groups may be linear or branched and of the formula:

C_(a)F_(2a+1)—, where a is at least 1, preferably at least 3, morepreferably 3-6; or may be have in-chain oxygen as in the formula:

C_(a)F_(2a+1)—(O—C_(b)F_(2b))_(c)—, where a is at least 1, b is at least2, and c may be a number from 1 to 10;

or may have in-chain nitrogen as in the formula:

C_(a)F_(2a+1)N(C_(a)F_(2a+1))—C_(b)F_(2b)—, where each a is at least 1,and b is at least 2. Preferably, each of the perfluoroalkyl orperfluoroalkylene groups are selected from C₃-C₆.

It has been reported that certain perfluorooctyl-containing compounds(C₈F₁₇—) may tend to bio-accumulate in living organisms; this tendencyhas been cited as a potential concern regarding some fluorochemicalcompositions. For example, see U.S. Pat. No. 5,688,884 (Baker et al.).As a result, there is a desire for fluorine-containing compositionseffective in providing desired functional properties, e.g., water- andoil-repellency, surfactant properties, etc. while eliminating moreeffectively from biological systems. However, it has also been assertedthat only perfluoroalkyl groups of the formula F(CF₂)_(n)— have six orgreater carbons have the self-alignment capability to achieve usefulperformance, while shorter chains, e.g. C₄F₉— lack the self-alignmentnecessary for good performance. See Phillips and Dettree, J. Col andInterface Sci., vol. 56(2), August 1976.

Therefore it remains a challenge to provide shorter chain perfluoroalkylcompositions that are less bioaccumulative, while maintain the requisiteperformance.

In some preferred embodiments, the present fluoroalkylsilane compoundsand coating compositions provide the necessary performance even with theshorter C₃-C₆ perfluoroalkyl groups. Furthermore, the short chainperfluorocarboxylic acids (the presumed intermediate degradationproducts) are less toxic and less bioaccumulative than the longer chain(C₈) homologues. For these reasons, the R_(f) groups is preferablyselected from C₃-C₆ perfluoroalkyl (and/or perfluoroalkylene) groups.The present invention provides novel fluoroalkyl alkenes, havingmultiple fluoroalkyl groups pendent from the same branch, increasing thefluoroalkyl content, while reducing the chain length thereof.

The fluoroalkyl compounds of Formula I may be prepared by reaction of acompound of the formula:R_(f)—O—CF═CF₂  IIwith a terminally unsaturated polyol of the formula:(H—O—)_(x)—R*CH═CH₂,  IIIin the presence of a base catalyst as described in US20050113609,and where R*, subscript x and R_(f) are as previously defined.

The perfluorovinyl ether of Formula II, in turn, may be prepared byfluoride ion catalyzed addition of a perfluorinated acid fluoride tohexafluoropropylene oxide, followed by decarboxylation, according to thetechniques describe in U.S. Pat. No. 6,255,536 (Worm et al.),incorporated herein by reference. Perfluorinated acid fluoride may beobtained from hexafluoropropene oxide by reaction with a metal fluoride.Alternatively, the perfluorinated acid fluorides may be prepared byelectrochemical fluorination of alcohols, acids or esters as known inthe art, for example as described in U.S. Pat. No. 6,482,979 (Hintzer etal.), incorporated herein by reference.

Commercial available perfluorovinyl ethers of Formula II are, forexample, CF₃OCF═CF₂, CF₃CF₂CF₂OCF═CF₂ and CF₃OCF₂CF₂CF₂OCF═CF₂.

With reference to Formula III, R* may be any (hetero)hydrocarbyl group,Preferably R* is an alky or aryl group.

The perfluorovinyl ethers of Formula II may be used to preparepolyfluoroalkylated silicon compounds, including silanes and siliconesof the general formula[R_(f)—O—CHFCF₂—O]_(x)—R*—Si*,  IVwhereinR_(f) is a perfluoroalkyl group, as previously defined;R* is (hetero)hydrocarbyl group of valence x+1;subscript x is at least two; andSi* is a silane or silicone group.

More particularly, the present disclosure provides fluoroalkyl silanesof the formula:[R_(f)—O—CHFCF₂—O]_(x)—R*—Si(X)_(q)R² _(3-q),  VwhereinR_(f) is a perfluoroalkyl group, as previously defined;R* is (hetero)hydrocarbyl group of valence m+1;subscript x is at least two;X is a hydrolysable group;R² is a C₁-C₄ alkyl group; andsubscript q is 1 to 3.

The present disclosure also provides fluoroalkyl silicones of theformula:

each R¹ is independently an alkyl or aryl;R_(f) is a perfluoroalkyl group, optionally substituted by one or morein-chain —O—, —S— or —NR_(f) ¹— heteroatoms, where R_(f) ¹ is aperfluoroalkyl, preferably a C₁-C₆ perfluoroalkyl;R³ is —H, —OR⁴; where R⁴ is a C₁-C₄ alkyln is 0 to 2000;m may be zero;p may be zero,n+m+p is at least one;q is at least 3;R⁵ is H, alkyl, aryl —R*[—O—CF₂CHF—O—R_(f)]_(x), or R³;R* is a (hetero)hydrocarbyl groups of valence x+1;x is at least 2;wherein the fluoroalkyl silicone has at least one fluorinated group ofthe formula —R*[—O—CF₂CHF—O—R_(f)]_(x).

The silicone compounds of Formula IV is prepared by hydrosilation of afluorinated compound of the formula:[R_(f)—O—CHFCF₂—O]_(x)—R*—CH═CH₂,  IwhereinR_(f) is a perfluoroalkyl group, as previously described;subscript x is at least two;R* is (hetero)hydrocarbyl group of valence m+1,with a hydrosilane of the formula:H—Si*,  VIIin the presence of a hydrosilation catalyst, where Si* is a reactivesilane or silicone.

More particularly, the fluoroalkyl silanes of formula V may be preparedby hydrosilation with a hydrosilane of the formula:H—Si(X)_(q)R² _(3-q),  VIIIin the presence of a hydrosilation catalyst, whereX is a hydrolysable group;R² is an alkyl group or an aryl group; andq is 1 to 3.

The X groups can be the same or different and are capable ofhydrolyzing, for example, in the presence of water, optionally underacidic or basic conditions, to produce groups capable of undergoing acondensation reaction (for example, hydroxysilyl groups). Desirably,each X is independently selected from hydroxyl, halogen, alkoxy,acyloxy, aryloxy, and combinations thereof; most desirably, each X isindependently alkoxy). It will be appreciated that the X groups willhydrolyze in the presence of water or moisture, and some portion of theX groups may be hydrolyzed to —OH groups, which may then form siloxanelinkages with each other or with hydroxyl-containing substrate surfacevia dehydration condensation reactions.

The preferred hydrosilane of the formula VII is selected from H—SiCl₃,H—Si(OMe)₃ and H—Si(OCH₂CH₃)₃.

The fluoroalkyl silicones of Formula VIII may be prepared byhydrosilation with a hydrosilicone of the formula:

whereeach R¹ is independently an alkyl or aryl;n is 0 to 2000; preferably at least 10;v may be zero;R⁶ is H, alkyl or aryl;with the proviso that the hydrosilicone contains at least one Si—Hgroup, preferably at least two Si—H groups. Thus the silicone unit withthe subscript “v” of Formula III may be at least one, preferably atleast 2, and/or R⁶ can be H.

Examples of useful Si—H group containing silicones of Formula IX includehydride terminated polydimethylsiloxanes having the formulaHMe₂SiO(SiMe₂O)_(n)SiMe₂H (CAS 70900-21-9); hydride terminatedmethylhydrosiloxane-dimethylsiloxane copolymers having the formulaHMe₂SiO(SiMe₂O)_(n)(SiMeHO)_(q)SiMe₂H (CAS 69013-23-6);trimethylsiloxane terminated polyethylhydrosiloxanes having the formulaMe₃SiO(SiMeHO)_(q)SiMe₃ (CAS 63148-57-2); trimethylsiloxane terminatedmethylhydrosiloxane-dimethylsiloxane copolymers having the formulaMe₃SiO(SiMe₂O)_(n)(SiMeHO)_(q)SiMe₃ (CAS 68037-59-2); triethylsiloxaneterminated polyethylhydrosiloxanes having the formulaEt₃SiO(SiEtHO)_(q)SiEt₃ (CAS 24979-95-1); hydride terminatedpoly(phenyl-dimethylhydrosiloxysiloxanes) having the formulaHSiMe₂O(SiPh(OSiMe₂H)O)_(q)SiMe₂H; all commercially available fromvendors such as, for example, Gelest, Inc. or Dow Corning Corp. withdifferent molecular weights.

All or a portion of the Si—H groups of the hydrosilicone may be reactedwith the alkenyl ether of Formula I. In some embodiments, unreactedhydrosilyl (Si—H) groups may be converted to other useful functionalgroups, as described herein. In the presence of the hydrosilylationcatalyst, the compounds of Formula I are hydrosilated by thehydrosilicone of Formulas VIII or IX to produce the fluoroalkylsilicones of Formulas V or X respectively. All or a portion of the Si—Hgroups may undergo the hydrosilylation with the compound of Formula I.

In the following Scheme I, subscript “v” represent the number oforiginal in-chain hydrosilane units, m the number of those in-chainunits substituted by hydrosilylation, and subscript s is the number ofin-chain Si—H groups remaining. In addition, where R⁶ is H, all or aportion of those terminal Si—H groups may undergo hydrosilylation toprovide terminal R_(f) groups in the R⁷. In some embodiments, all of theSi—H groups, whether terminal or in-chain, will be converted to—R*—[OCF₂CHFOR_(f)]_(x) groups.

each R′ is independently an alkyl or aryl;R_(f) is a perfluoroalkyl group, as previously described;R³ is —H, —OR⁴; where R⁴ is a C₁-C₄ alkyln is 0 to 2000;m may be zero;s may be zero;n+m+p is at least one;R⁵ is H, alkyl, aryl —R*[—O—CF₂CHF—O—R_(f)]_(x), or R³;R* is a (hetero)hydrocarbyl groups of valence x+1;x is at least 2;wherein the fluoroalkyl silicone has at least one fluorinated group ofthe formula —R* [—O—CF₂CHF—O—R_(f)]_(x).

Alternatively, the fluoroalkyl silicones of the formula VI can be madeby condensation of the fluorlkylsilane of Formula V with one or moredihydrocarbydialkoxysilanes, such as dimethyldimethoxysilane.

Regarding the product of Formula X of Scheme I, the Si—H functionalfluoroalkyl silicones may be used as a crosslinking agent, such as tothermally crosslink with silicones or fluorinated silicones having aplurality of ethylenically unsaturated bonds in a subsequenthydrosilylation reaction. In some embodiments, the fluoroalkyl siliconemay be subsequently crosslinked by vinyl substituted silicones: i.e.silicone having a plurality of vinyl groups.

The non-fluorinated organopolysiloxane polymers (vinyl silicones)comprising an average of at least two ethylenically unsaturated organicgroups may be formulated with the fluoroalkyl silicone of Formula V. Insome embodiments, the non-fluorinated organopolysiloxane polymer has avinyl equivalent weight of no greater than 60,000 grams per equivalent,e.g., no greater than 20,000, or even no greater than 10,000 grams perequivalent. In some embodiments, the non-fluorinated organopolysiloxanepolymer has a vinyl equivalent weight of 2000 to 5000 grams perequivalent, e.g., 2000 to 4000 grams per equivalent, or even 2500 to3500 grams per equivalent.

Exemplary non-fluorinated organopolysiloxane polymers include thosecomprising a triorganosiloxy end blocked polydiorganosiloxane polymer.In some embodiments, the non-fluorinated organopolysiloxane polymercomprises R₂SiO_(2/2) units (i.e., “D” units) and R₃SiO_(1/2) units(i.e., “M” units), wherein each R group independently represents asaturated or ethylenically unsaturated, substituted or unsubstitutedhydrocarbon radical, provided that at least two R groups containterminal ethylenic unsaturation.

The ethylenically unsaturated radicals are independently selected fromthe group consisting of the vinyl radical and higher alkenyl radicalsrepresented by the formula —R′—CH═CH wherein R′ denotes —(CH₂)_(w)—; andw has the value of 1-48.

In some embodiments, trace amounts of non-linear siloxane units, i.e.,SiO_(4/2) units (i.e., “Q” units) and RSiO_(3/2), units (i.e., “T”units); may be present wherein R is as described above. In someembodiments, trace amounts of other silicon-bonded radicals, such ashydroxyl and alkoxyl may also be present.

Exemplary non-fluorinated organopolysiloxane polymer comprising anaverage of at least two ethylenically unsaturated organic groups includethose having the formula M^(vi)D_(x)M^(vi), wherein M represents Munits, D represents D units, the superscript “vi” indicates the presenceof vinyl-functional groups, and x is the degree of polymerization.Commercially available M^(vi)D_(x)M^(vi), non-fluorinatedorganopolysiloxane polymers include those available under the tradedesignations DMS-V from Gelest Inc. (e.g., DMS-V03, DMS-V05, DMS-V21,DMS-V22, DMS-V25, DMS-V35, and DMS-V41).

Examples of useful silicone having a plurality of vinyl groups includevinyl terminated polydimethylsiloxanes having the formulaH₂C═CHSiMe₂O(SiMe₂O)_(n)SiMe₂CH═CH₂ (CAS 68083-19-2); vinyl terminateddimethylsiloxane-diphenylsiloxane copolymers having the formulaH₂C═CHSiMe₂O(SiMe₂O)_(n)(SiPh₂O)_(m)SiMe₂CH═CH₂ (CAS: 68951-96-2); vinylterminated polyphenylmethylsiloxanes having the formulaH₂C═CHSiMePhO(SiMePhO)_(n)SiMePhCH═CH₂ (CAS: 225927-21-9);vinyl-phenylmethyl terminated vinylphenylsiloxane-methylphenylsiloxanecopolymers (CAS: 8027-82-1); vinyl terminatedtrifluoropropylmethylsiloxane-dimethylsiloxane copolymers having theformula H₂C═CHSiMePhO(SiMe₂O)_(n)(SiMe(CH₂CH₂CF₃)O)_(m)SiMePhCH═CH₂(CAS: 68951-98-4);H₂C═CHSiMe₂O—(SiMe₂O)_(n)(SiMe(CH₂CH₂CF₃)O)_(m)SiMe₂CH═CH₂,H₂C═CHSiMe₂O—(SiMe₂O)_(n)(SiMe(CH₂CH₂C₄F₉)O)_(m)SiMe₂CH═CH₂, vinylterminated dimethylsiloxane-diethylsiloxane copolymers having theformula H₂C═CHSiMe₂O(SiMe₂O)_(n)(SiEt₂O)_(n)SiMe₂CH═CH₂; trimethylsiloxyterminated vinylmethylsiloxane-dimethylsiloxane copolymersMe₃SiO(SiMe₂O)_(n)(SiMe(CH═CH₂)O)_(m)SiMe₃ (CAS: 67762-94-1); vinylterminated vinylmethylsiloxane-dimethylsiloxane copolymers having theformula H₂C═CH(SiMe₂O)_(n)(SiMeCH═CH₂O)_(m)SiMe₂CH═CH₂ (CAS:68063-18-1); vinylmethylsiloxane homopolymers (cyclic and linear) havingthe formula Me₃SiO(SiMe(CH═CH₂)O)_(n)SiMe₃; and vinyl T-structurepolymers having the formula MeSi[O(SiMe₂O)_(m)SiMe₂CH═CH_(2]3); allcommercially available from vendors such as, for example, Gelest, Inc.,Morrisville, Pa. or Dow Corning Corp., Midland, Mich. Additional usefulsilicones having a plurality of vinyl groups include a vinyl-terminatedfluorosilicone that is commercially available under the tradedesignations “SYL-OFF Q2-7785” and “SYL-OFF Q2-7786” from Dow CorningCorp.

In some embodiments, the Si—H group of Formula X, Scheme 1 may beconverted to alkyl groups by subsequent hydrosilylation of an olefin ofthe formula: CH₂═CHCH₂—R⁴, where R⁴ is H or C₁-C₅₀ alkyl in the presenceof a hydrosilylation catalyst.

Again with regard to the silicone of Formula IX, Scheme I, the Si—Hgroups may be converted to alkoxide groups (Si—H→Si—OR⁴) and thealkoxy-functional fluoroalkyl silicone can be subsequentlyhydrolysis-condensation crosslinked by siloxane formation. Generally,the hydrides are reacted with an alcohol of the formula R⁴—OH to convertall or a portion of the Si—H groups to Si—OR⁴ groups, where R⁴ is aC₁-C₅₀ alkyl, preferably a short alkyl group (C₁-C₁₆, preferably C₁-C₄)for easy hydrolysis. Thus the present disclosure provides crosslinkable,fluoroalkyl silicones of the formula:

whereinn is 0 to 2000;m may be zero, preferably at least one;s may be zero;t may be zero, preferably at least one;R⁸ is H, alkyl or aryl, —R*—[OCF₂CHFOR_(f)]_(x) or OR⁴, where R⁴ isC₁-C₅₀ alkyl;x is at least 2; andR_(f) is a perfluoroalkyl group, as previously defined;with the proviso that the silicone contains at least one, preferably atleast two Si—OR⁴ groups and the silicone contains at least one—R*[—O—CF₂CHF—O—R_(f)]_(x) group.

In Formula XI, the unit with the subscript t may be at least one,preferably at least two, and/or R⁸ may be —OR⁴. Further, if only aportion of the Si—H groups are converted to alkoxysilane groups(Si—OR⁴), then s may be at least one, and/or a portion of R⁸ may be H.Further, the unit with the subscript m may be at least one, and/or aportion of the R⁸ groups may be —R*[—O—CF₂CHF—O—R_(f)]_(x). In someembodiments R⁴ is lower-chain alkyl (C₁-C₁₆, preferably C₁-C₄). In otherembodiments R⁴ is long-chain alkyl (C₁₈-C₅₀)

Subsequently, these alkoxide groups (Si—OR⁴) may be hydrolyzed bymoisture, then crosslinked by dehydration, which can be catalyzed by aacid, or acid from a photoacid generator (PAG) initiated by photoirradiation, or a thermal acid generator initiated by heating to formsiloxane Si—O—Si crosslinked polymers. The acid generator is preferablyfree of amines or ammonium compounds. The crosslinking of the alkoxidesubstituted silicones by photo irradiation in the presence of PAG isdescribed in U.S. Pat. No. 6,129,980 or WO 9840439 (Liu et al.),incorporated herein by reference.

The conversion of all or a portion of the Si—H groups in the silicone toalkoxide groups by reacting the hydropolysiloxane with an alcohol in thepresence of at least one of a Pd(0) and Pt(0) catalyst according to themethods of U.S. 2013074130 (Rathore et al.) and incorporated herein byreference.

A wide variety of acid generating materials can be used in the practiceof the invention to catalyze the moisture curing reaction, includingonium salts such as sulfonium and iodonium salts. Activating the acidgenerating material liberates an acid that initiates and acceleratescrosslinking of the moisture-curable composition through the formationof Si—O—Si crosslinks. Activation may be accomplished by irradiating thecomposition with, for example, ultraviolet, visible light, electron beamor microwave radiation. While heat may be used to activate the acidgenerating material, the compositions of the invention advantageously donot require this and thereby can avoid undesirable damage to heatsensitive substrates.

Although the acid generating material described above is preferred dueto the controlled curability it provides, it has been found thatcondensation catalysts, such as strong organic acids, weak Lewis acids,weak organic bases and metal chelates can also be used in thepreparation of the novel silicone pressure-sensitive adhesive. Anotherpreferred class of condensation catalyst is the strong organic acidshaving pKa values of less than about 3 and the anhydrides and ammoniumsalts thereof described in U.S. Pat. No. 5,286,815. Examples of usefulstrong organic acids and derivatives include trichloroacetic acid,cyanoacetic acid, malonic acid, nitroacetic acid, dichloroacetic acid,difluoroacetic acid, trichloroacetic anhydride, dichioroaceticanhydride, difluoroacetic arthydride, triethylammonium trichloroacetate,trimethylammonium trichloroacetate, and mixtures thereof.

The condensation catalyst or an acid generating material is used inamounts of about 0.5 to about 20 parts by weight, based on 100 parts byweight of the alkoxy functional silicone.

The fluoroalkyl silicone of Formula XI contains both Si—OR⁴ and Si—Hfunctional groups are dual curable, which may be controllably curedinitially via Si—H with a vinyl silicone, then moisture or photo-acidcured from Si—OR⁴ or vice versa.

The fluoroalkyl silicones of the Formulas have a M_(w) of at least 400,preferably at least 1000. In some embodiments, the M_(w) may be 2000 orgreater. In some embodiments, the M_(w) may be limited to 1,000,000 orless; preferably limited to 500,000 or less. In some embodiments n, mand p are each greater than one and where the ratio of n to m is greaterthan one, preferably the ratio of n to m is greater than 10. In someembodiments, R³ is H, and the ratio of m to p is from 100:0 to 5:95. Insome embodiments, R³ is OR⁴ (prepared as described herein).

Regarding the hydrosilation reaction, numerous patents teach the use ofvarious complexes of cobalt, rhodium, nickel, palladium, or platinum ascatalysts for hydrosilylation between a compound containingsilicon-bonded hydrogen such as formula III and a compound containingterminal aliphatic unsaturation. For example, U.S. Pat. No. 4,288,345(Ashby et al) discloses as a catalyst for hydrosilylation reactions aplatinum-siloxane complex. Additional platinum-siloxane complexes aredisclosed as catalysts for hydrosilylation reactions in U.S. Pat. Nos.3,715,334, 3,775,452, and 3,814,730 (Karstedt et al). U.S. Pat. No.3,470,225 (Knorre et al) discloses production of organic siliconcompounds by addition of a compound containing silicon-bonded hydrogento organic compounds containing at least one non-aromatic double ortriple carbon-to-carbon bond using a platinum compound of the empiricalformula PtX₂(RCOCR′COR″)₂ wherein X is halogen, R is alkyl, R′ ishydrogen or alkyl, and R″ is alkyl or alkoxy.

The catalysts disclosed in the foregoing patents are characterized bytheir high catalytic activity. Other platinum complexes for acceleratingthe aforementioned thermally-activated addition reaction include: aplatinacyclobutane complex having the formula (PtCl₂C₃H₆)₂ (U.S. Pat.No. 3,159,662, Ashby); a complex of a platinous salt and an olefin (U.S.Pat. No. 3,178,464, Pierpoint); a platinum-containing complex preparedby reacting chloroplatinic acid with an alcohol, ether, aldehyde, ormixtures thereof (U.S. Pat. No. 3,220,972, Lamoreaux); a platinumcompound selected from trimethylplatinum iodide and hexamethyldiplatinum(U.S. Pat. No. 3,313,773, Lamoreaux); a hydrocarbyl or halohydrocarbylnitrile-platinum (II) halide complex (U.S. Pat. No. 3,410,886, Joy); ahexamethyl-dipyridine-diplatinum iodide (U.S. Pat. No. 3,567,755,Seyfried et al); a platinum curing catalyst obtained from the reactionof chloroplatinic acid and a ketone having up to 15 carbon atoms (U.S.Pat. No. 3,814,731, Nitzsche et al); a platinum compound having thegeneral formula (R′)PtX₂ where R′ is a cyclic hydrocarbon radical orsubstituted cyclic hydrocarbon radical having two aliphaticcarbon-carbon double bonds, and X is a halogen or alkyl radical (U.S.Pat. No. 4,276,252, Kreis et al); platinum alkyne complexes (U.S. Pat.No. 4,603,215, Chandra et al.); platinum alkenylcyclohexene complexes(U.S. Pat. No. 4,699,813, Cavezzan); and a colloidal hydrosilylationcatalyst provided by the reaction between a silicon hydride or asiloxane hydride and a platinum (0) or platinum (II) complex (U.S. Pat.No. 4,705,765, Lewis).

Although these platinum complexes and many others are useful ascatalysts in processes for accelerating the hydrosilation, processes forpromoting the ultraviolet or visible radiation-activated additionreaction between these compounds may be preferable in some instances.Platinum complexes that can be used to initiate ultravioletradiation-activated hydrosilation reactions have been disclosed, e.g.,platinum azo complexes (U.S. Pat. No. 4,670,531, Eckberg);(η⁴-cyclooctadiene)diarylplatinum complexes (U.S. Pat. No. 4,530,879,Drahnak); and (η⁵-cyclopentadienyl)trialkylplatinum complexes (U.S. Pat.No. 4,510,094, Drahnak). Other compositions that are curable byultraviolet radiation include those described in U.S. Pat. Nos.4,640,939 and 4,712,092 and in European Patent Application No. 0238033.U.S. Pat. No. 4,916,169 (Boardman et al) describes hydrosilylationreactions activated by visible radiation. U.S. Pat. No. 6,376,569 (Oxmanet al.) describes a process for the actinic radiation-activated additionreaction of a compound containing silicon-bonded hydrogen with acompound containing aliphatic unsaturation, said addition being referredto as hydrosilylation, the improvement comprising using, as a platinumhydrosilylation catalyst, an(η⁵-cyclopentadienyl)tri(σ-aliphatic)platinum complex, and, as areaction accelerator, a free-radical photoinitiator capable of absorbingactinic radiation, i.e., light having a wavelength ranging from about200 nm to about 800 nm. The process can also employ, as a sensitizer, acompound that absorbs actinic radiation, and that is capable oftransferring energy to the aforementioned platinum complex or platinumcomplex/free-radical photoinitiator combination, such that thehydrosilylation reaction is initiated upon exposure to actinicradiation. The process is applicable both to the synthesis of lowmolecular weight compounds and to the curing of high molecular weightcompounds, i.e., polymers.

This disclosure further provides coating composition comprising thefluoroalkyl silicon compounds in a solvent. Generally, the coating isformulated in a solvent or mixed solvents for easy use at theconcentration of 0.01 to 50 wt %; preferably at 0.1 to 20%.

For crosslink or curing of the coating, moisture is needed, either byaddition of limited water to the coating formulation or absorption ofmoisture from air after coating on substrates. To accelerate the curing,a acid or base catalyst may be optionally presented in the formulation.

In some embodiments, the coating composition may further comprise acrosslinking agent for the fluoroalkylsilane. A class of usefulcrosslinkers includes compounds that can be represented by the followinggeneral formula:Si(X¹)_(z)R¹² _(4-z),  XIIwherein each X¹ is independently hydroxyl, a hydrolyzable group, or acombination thereof; each R¹² is independently a C₁-C₄ alkyl group; z isan integer of 1, 2, 3 or 4. Preferences for X¹ and R′² include those setforth above for the X and R groups of Formulas V and VIII. Thecrosslinkers can be included in the surface treatment composition in anyof a wide range of amounts (for example, from about 1 to 20 weightpercent), depending, for example, upon the particular application andthe desired properties. Most preferred are tetralkoxysilanes, such ascommercial available tetraethoxysilane, alone or in a mixture withtrialkoxysilanes.

A variety of non-functional inorganic oxide particulate solutions ordispersions can be used in the coating composition. The particles aretypically substantially spherical in shape and relatively uniform insize. The particles can have a substantially monodisperse sizedistribution or a polymodal distribution obtained by blending two ormore substantially monodisperse distributions. The inorganic oxideparticles are typically non-aggregated (substantially discrete), asaggregation can result in precipitation of the inorganic oxide particlesor gelation of the composition.

The inorganic oxide particles are typically colloidal, having an averageparticle diameter of about 0.001 to about 0.2 micrometers, less thanabout 0.05 micrometers, and less than about 0.03 micrometers. These sizeranges facilitate dispersion of the inorganic oxide particles into thecoating composition with desirable surface properties and opticalclarity. The average particle size of the inorganic oxide particles canbe measured using transmission electron microscopy to count the numberof inorganic oxide particles of a given diameter.

Inorganic oxide particles include colloidal silica, colloidal titania,colloidal alumina, colloidal zirconia, colloidal vanadia, colloidalchromia, colloidal iron oxide, colloidal antimony oxide, colloidal tinoxide, and mixtures thereof. The inorganic oxide particles can consistessentially of or consist of a single oxide such as silica, or cancomprise a combination of oxides, such as silica and aluminum oxide, ora core of an oxide of one type (or a core of a material other than ametal oxide) on which is deposited an oxide of another type. Silica is acommon inorganic particle for general applications.

The inorganic oxide particles are often provided in the form of a solcontaining a colloidal dispersion of inorganic oxide particles in liquidmedia including water and isopropanol as solvent. The sol can beprepared using a variety of techniques and in a variety of formsincluding hydrosols (where water serves as the liquid medium),organosols (where organic liquids so serve), and mixed sols (where theliquid medium contains both water and an organic liquid), e.g., asdescribed in U.S. Pat. No. 5,648,407 (Goetz et al.); U.S. Pat. No.5,677,050 (Bilkadi et al.) and U.S. Pat. No. 6,299,799 (Craig et al.),the disclosure of which is incorporated by reference herein. Aqueoussols (e.g. of amorphous silica) can be employed. Sols generally containat least 2 wt-%, at least 10 wt-%, at least 15 wt-%, at least 25 wt-%,and often at least 35 wt-% colloidal inorganic oxide particles based onthe total weight of the fluorosilane in the coating formulation. Theamount of colloidal inorganic oxide particle is typically no more than50 wt-%. Most water is generally removed from the aqueous sols prior toformulating with fluorosilane to prevent premature hydrolysis forsufficient shelf life stability.

The coating composition can be prepared by mixing the inorganic oxideparticle solution, and other optional ingredients with the curablefluorosilane composition. The resulting composition after applied to asubstrate usually is dried to remove substantially all of the solventand/or water from the formulation or generated during the silanoldehydration condensation reaction.

Some embodiments, partially surface-modified inorganic particles,preferably nanoparticles (having an average particle size of less than100 nanometers) may be used. These particles and nanoparticles areprepared from colloidal materials from the group of silica, zinc oxide,titania, alumina, zirconia, vanadia, chromia, iron oxide, antimonyoxide, tin oxide, other colloidal metal oxides, and mixtures thereof,modified such that the particles can be easily formulated or dispersedwith fluorosilane formulation; these particles can comprise essentiallya single oxide such as silica or can comprise a core of an oxide of onetype (or a core of a material) on which is deposited the oxide ofanother type. The particles have an average particle diameter of 5 toabout 1000 nm, preferably less than 100 nanometers, more preferably 10to 50 nm. Average particle size can be measured using transmissionelectron microscopy to count the number of particles of a givendiameter. Additional examples of suitable colloidal silicas aredescribed in U.S. Pat. No. 5,126,394, incorporated herein by reference.Such particles are described in U.S. Pat. Nos. 6,353,037, and 6,462,100(Thunhorst et al.), and U.S. Pat. No. 6,329,058 (Arney et al.) and areincorporated herein by reference. The fluorosilane of formula I may alsobeen used for partial modification of inorganic particles.

The resulting curable coating composition can have a relatively longshelf life in the absence of moisture. The components of the compositioncan be in the form of relatively viscous liquids that can be used in thesurface treatment process of the invention in neat form or, preferably,in admixture with commonly-used solvents (for example, alkyl esters,ketones, alkanes, alcohols, and the like, and mixtures thereof).

In some embodiments, the coating composition further includes at leastone organic solvent that can dissolve or suspend at least about 0.1percent by weight of the fluoroalkylsilane of Formulas V and VI andsilicate components of Formula XII, based upon the total weight of thesurface treatment composition. In some embodiments, it can be desirablethat the solvent or mixture of solvents have a solubility for water ofat least about 1 percent by weight, and for certain of theseembodiments, a solubility for acid of at least about 5 percent byweight. When solvent is used, useful concentrations of the componentscan vary over a wide range (for example, from about 0.01 or 0.1 or 1 toabout 90 weight percent), depending upon the solubility of thecomponents, the application method utilized, the nature of thesubstrate, and the desired surface treatment characteristics.

Suitable organic solvents for use in the surface treatment compositioninclude aliphatic alcohols such as, for example, methanol, ethanol, andisopropanol; ketones such as acetone and methyl ethyl ketone; esterssuch as ethyl acetate and methyl formate; ethers such as diethyl ether,diisopropyl ether, methyl t-butyl ether, and dipropylene glycolmonomethyl ether (DPM); hydrocarbons solvents such as alkanes, forexample, heptane, decane, and other paraffinic solvents; perfluorinatedhydrocarbons such as perfluorohexane and perfluorooctane; fluorinatedhydrocarbons, such as pentafluorobutane; hydrofluoroethers such asmethyl perfluorobutyl ether and ethyl perfluorobutyl ether; and thelike; and combinations thereof. Preferred solvents include aliphaticalcohols, perfluorinated hydrocarbons, fluorinated hydrocarbons,hydrofluoroethers, and combinations thereof (more preferably, aliphaticalcohols, hydrofluoroethers, and combinations thereof; most preferably,hydrofluoroethers and combinations thereof).

The coating composition may comprise:

a) 0.25 to 10 wt. % fluoroalkylsilane of Formulas V or VI;

b) 0 to 20 wt. % inorganic particulate filler;

c) 0 to 20 wt. % a silane crosslinker of Formula XII;

d) 0 to 10 wt. % of an acid catalyst;

in an organic solvent.

The coating composition can be used as a fluorochemical surfacetreatment to impart a degree of hydrophobicity and/or oleophobicity to avariety of substrates. Substrates suitable for use in the process of theinvention (and for preparing the surface-treated articles of theinvention) include those having at least one surface comprising amaterial that is solid and preferably substantially inert to any coatingsolvent that is used. Preferably, the surface treatment can adhere tothe substrate surface through chemical interactions, physicalinteractions, or a combination thereof (more preferably, a combinationthereof).

Suitable substrates can comprise a single material or a combination ofdifferent materials and can be homogeneous or heterogeneous in nature.Useful heterogeneous substrates include coated substrates comprising acoating of a material (for example, a glass or a primer) borne on aphysical support (for example, a polymeric film).

Useful substrates include those that comprise wood, glass, minerals (forexample, both man-made ceramics such as concrete and naturally-occurringstones such as marble and the like), polymers (for example,polycarbonate, polyester, polyacrylate, and the like), metals (forexample, copper, silver, aluminum, iron, chromium, stainless steel,nickel, and the like), metal alloys, metal compounds (for example, metaloxides and the like), leather, parchment, paper, textiles, paintedsurfaces, and combinations thereof. Preferred substrates include thosehaving siliceous surfaces in either primed or unprimed form. Preferredsubstrates include glass, minerals, wood, metals, metal alloys, metalcompounds, primed polymers, and combinations thereof (more preferably,glass, minerals, metals, metal alloys, metal compounds, primed polymers,and combinations thereof; most preferably, glass, minerals, andcombinations thereof).

Typically the substrate will be chosen based in part on the desiredoptical and mechanical properties for the intended use. Such mechanicalproperties typically will include flexibility, dimensional stability andimpact resistance. The substrate thickness typically also will depend onthe intended use. For most applications, substrate thicknesses of lessthan about 0.5 mm are preferred, and more preferably about 0.02 to about0.2 mm. Self-supporting polymeric films are preferred. The polymericmaterial can be formed into a film using conventional filmmakingtechniques such as by extrusion and optional uniaxial or biaxialorientation of the extruded film. The substrate can be treated toimprove adhesion between the substrate and the coating layer, e.g.,chemical treatment, corona treatment such as air or nitrogen corona,plasma, flame, or actinic radiation. If desired, an optional tie layeror primer can be applied to the substrate and/or coating layer toincrease the interlayer adhesion.

For best efficacy, the substrate has a surface with groups capable offorming covalent bonds to the silane groups (for example, hydroxylgroups). In some embodiments, the suitability of the surface of thesubstrate can be improved by deposition of a primer or by some otherphysical or chemical surface modification technique. Plasma depositiontechniques can be used, if desired.

The coating composition can be applied separately or in combination(preferably, in combination) to at least a portion of at least one majorsurface of the substrate in essentially any manner (and with essentiallyany thickness) that can form a useful coating. Useful applicationmethods include coating methods such as dip coating, spin coating, spraycoating, wiping, roll coating, brushing, spreading, flow coating, andthe like, and combinations thereof.

Typically, the coating composition can be coated on the substrate suchthat after an optional drying, a monolayer of the surface treatmentcomposition results. Typically, such a monolayer can be from about 0.001to about 1 micrometer thick (more typically, from about 0.001 to about0.10 microns thick).

After application to the substrate, the coating can be cured by exposureto heat and/or moisture. Moisture cure can be effected at temperaturesranging from room temperature (for example, about 20° C.) up to about80° C. or more. Moisture curing times can range from a few minutes (forexample, at the higher temperatures) to hours (for example, at the lowertemperatures).

For the preparation of a durable coating, sufficient water typically canbe present to cause hydrolysis of the hydrolyzable groups describedabove, so that condensation to form siloxane (Si—O—Si) groups betweenthefluoroalkylsilanes of Formula I and also the substrate. The water canbe, for example, present in the coating composition, adsorbed on thesubstrate surface, or in the ambient atmosphere. Typically, sufficientwater can be present for the preparation of a durable coating if thecoating method is carried out at room temperature in an atmospherecontaining water (for example, an atmosphere having a relative humidityof about 30 percent to about 50 percent). Preferably, the coatingcomposition can undergo chemical reaction with the surface of thesubstrate to form a durable coating through the formation of covalentbonds (including Si—O—Si groups).

Useful moisture curing catalysts for silane compounds are well-known inthe art and include organic or inorganic acids (for example, aceticacid, propionic acid, butyric acid, valeric acid, maleic acid, stearicacid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid,hydrochloric acid, and the like, and combinations thereof), metalcarboxylates, metal acetylacetonate complexes, metal powders, peroxides,metal chlorides, organometallic compounds, and the like, andcombinations thereof.

When used, the acid catalysts can be present in amounts ranging fromabout 0.01 to about 10 weight percent (preferably, from about 0.25 toabout 10 weight percent; more preferably, from about 0.25 to about 5weight percent), based upon the total weight of catalyst and surfacetreatment composition).

A substrate to be coated can typically be contacted with the coatingcomposition at room temperature (typically from 20° C. to 30°.Alternatively, the coating composition can be applied to substrates thatare preheated at a temperature of, for example, between 60° C. and 150°C. Following application of the surface treatment composition, thecoated substrate can be dried and the resulting coating cured at ambienttemperature (for example, about 20° C. to about 30° C. or elevatedtemperature (for example, at about 40° C. to about 150° C.) for a timesufficient for the curing to take place.

Regarding the fluoroalkyl silanes of Formula V, the cured coating may bedescribed by the general formula:[R_(f) ²SiO_(3/2)]_(a)[SiO_(4/2)]_(b)[RSiO_(3/2)]_(c), whereR_(f) ² is [R_(f)—O—CHFCF₂—O-]_(x)R*- and the unit is derived from thefluoroalkylsilane of Formula V where subscript “q” is 3,[SiO_(4/2)] are units derived from the tetraalkoxysilanes;[RSiO_(3/2)] are units derived from the trialkoxysilanes. It will beappreciated that some siloxane bond formation will form with certainsubstrates.

The curable coating composition can be applied to articles comprisingone or more of the above-described substrates and then cured to formsurface treatments in the form of crosslinked hardcoats. The hardcoatscan exhibit surface and/or bulk properties that can be tailored byvarying the degree of crosslinking and by varying the natures andrelative amounts of the particulate filler. The hardcoats (with theiroften outstanding durability, adhesion, and repellency properties) canbe widely used for applications requiring durable low surface energycharacteristics (for example, anti-graffiti coatings for signs,buildings, transportation vehicles, and the like; easily cleanableand/or anti-smudge coatings for glass, paper, clothes, metals, ceramictiles, electronic devices, optical devices, and the like; mold releasecoatings for polymer or composite molding; and the like).

A useful hardcoat coating composition comprises:

a) 0.5 to 5 wt % fluoroalkylsilane of Formulas V or VI;

b) 1 to 10 wt % nanoparticle silica, and/or

c) 1 to 10 wt % silane crosslinker of Formula X.

In general, the method of coating comprises providing a substrate,coating at least a portion of the substrate with the coatingcomposition, optionally drying to remove water and/or solvent, andcuring the coating. The resulting coating articles are both oleo- andhydrophobic. In some embodiments the coating exhibits a having areceding water contact angle of at least 80°, or at least 90°.

Examples

Materials

Des- igna- tion Description Source HDO 5-Hexene-1,2-diol AldrichChemical [CH₂═CH(CH₂)₂CH(OH)CH₂OH], Company, Milwaukee, 90% WI ODO7-Octene-1,2-diol [CH₂═CH(CH₂)₄CH(OH)CH₂OH], 97% APDO3-Allyl-1,2-propanediol [CH₂═CHCH₂OCH₂CH(OH)CH₂OH], 99% TMPAETrimethylol propane allyl ether [CH₂═CHCH₂OCH₂CEt(CH₂OH)₂], 98% MG1,2-Dimethoxyethane GFS Chemicals, Powell, OH KOH Potassium hydroxide,pellets J. T. Baker, Center Valley, PA MV-3 C₃F₇OCF═CF₂ VWR, Batavia, ILMV-31 CF₃O(CF₂)₃OCF═CF₂ VWR, Batavia, IL PPVE-2 C₃F₇OCF(CF₃)CF₂OCF═CF₂Prepared as in Exam- ple 21 of U.S. Pat. No. 6,255,536 (Worm et al.)Test MethodsMethod for High Resolution GC-MS (HR GC-MS) Analysis Method

The sample was dissolved in chloroform at 1 mg/mL concentration and thesolution was used for analysis. High resolution accurate GasChromatography—Mass Spectrometry (GC-MS) analysis was carried out usingan Agilent High Definition 7200 GC-QTOF instrument (from AgilentTechnologies, Santa Clara, Calif.) equipped with GC 7890A system. Theanalyte molecules were ionized using both electron impact ionization(EI) and chemical ionization (CI). The sample components were separatedusing a 30 meter DB-5 ms capillary column (diameter: 250 μm, filmthickness: 0.25 μm). The column temperature was programmed to increasefrom 40° C. to 320° C. at a linear rate of 15° C./min with a final holdtime of 10 minutes. Helium was used as the carrier gas and the flow ratewas set at 1.1 mL/min. 1 μL of sample solution was introduced into theGC/MS system. The injector temperature was 280° C. and was operated insplit mode (split ratio 20:1 or 30:1).

General Procedure for Making Polyalkylated Alkenes

In a 200 ml Parr pressure reactor (form Parr Instrument Company, Moline,Ill.), 0.2 mol of ethylene-terminated (EPO), 30 g MG and 3.0 g KOHpellet were charged. Then, ˜0.44 mol perfluorinated vinyl ether (PVE,excess) was added, and the reactor was sealed. Under stirring (˜300RPM), the mixture was heated to 70° C. and reacted for 24 hours. Thepressure raised up to ˜50 psi (344.7 kPa) before dropping andstabilizing at ˜10 psi (68.9 kPa) from the excess PVE. The solution waspoured out after cooling to room temperature. Distillation to recover MGand unreacted PVE. Then the residue was washed with 0.1N HCl aqueoussolution, followed by two times washing with distilled water. The bottomlayer product solution was isolated and dried over anhydrous Na₂SO₄.Distillation in full vacuum, isolated the product. All products wereconfirmed by the analyses of ¹⁹F/¹H NMR and HR GC-MS spectra.

Examples 1-6 (EX1-EX6)

EX1-EX6 samples were prepared by using the general procedure for makingpolyalkylated alkenes described above. Table 1, below summarizes thereactants, yield and boiling points of products of each EX1-EX6. Thestructure and HR-GCMS analysis results are summarized in Table 2, below.

TABLE 1 Perfluorovinyl Example Polyol ether Yield (%)* Boiling Point EX1HDO PPVE-2 81.38 122-125° C./ 319.97 Pa EX2 HDO MV-3 88.5 113.5-115° C./1.93 kPa EX3 ODO MV-3 85.2 101-104° C./ 693.28 Pa EX4 APDO MV-3 87.898-100° C./ 333.31 Pa EX5 TMPAE MV-3 70.2 106-108.5° C./ 346.64 Pa EX6ODO MV-31 90.1 115-120° C./ 519.96 Pa *isolated yields based on EPO.

TABLE 2 Example Structure HRMS (Expected) EX1

C22 H12 F32 O6, 998.0528 (998.0461) EX2

C16 H12 F20 O4 666.0754 (666.0750) EX3

C18 H16 F20 O4 694.1065 (694.1067) EX4

C16 H12 F20 O5 682.0693 (682.0704) EX5

C19 H18F20 O5 724.1171 (724.1173) EX6

C20 H16 F24 O6 826.0919 (829.0902)

What is claimed:
 1. A polyfluoralkylated alkene of the formula:[R_(f)—O—CHFCF₂—O]_(x)—R*—CH═CH₂, wherein R_(f) is a perfluoroalkylgroup, optionally substituted by one or more in-chain —O—, —S— or—NR_(f) ¹— heteroatoms, where R_(f) ¹ is a perfluoroalkyl; subscript xis two; R* is a C₂-C₁₀ alkylene group.
 2. The alkene of claim 1 whereinR_(f) is a C₁-C₆ perfluorolkyl group.
 3. The alkene of claim 1, whereinR_(f) is selected from —CF₃, —CF₂CF₃, —C₃F₇, —C₄F₉, —C₅F₁₁, —C₆F₁₃,CF₃O(CF₂)₂CF₂—, (CF₃)₂N(CF₂)₂CF₂—, —CF₂CF(CF₃)₂ and C₃F₇OCF(CF₃)CF₂—. 4.The alkene of claim 1 wherein R_(f) is of the formulaC_(a)F_(2a+1)—(O—C_(b)F_(2b))_(c)—, where each of subscripts a and b isa number from 3 to 6, and c is a number from 1 to
 10. 5. The alkene ofclaim 1 wherein R_(f) is of the formulaC_(a)F_(2a+1)N(C_(a)F_(2a+1))—C_(b)F_(2b), where each of subscripts aand b is a number from 3 to 6.